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US2945065A - Process for the reduction of nitrocy-clohexane to cyclohexanone oxime - Google Patents

Process for the reduction of nitrocy-clohexane to cyclohexanone oxime Download PDF

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Publication number
US2945065A
US2945065A US751819A US75181958A US2945065A US 2945065 A US2945065 A US 2945065A US 751819 A US751819 A US 751819A US 75181958 A US75181958 A US 75181958A US 2945065 A US2945065 A US 2945065A
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Prior art keywords
cyclohexanone oxime
salt
carbon monoxide
nitrocyclohexane
pressure
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US751819A
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Donaruma Lorraine Guy
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EIDP Inc
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EI Du Pont de Nemours and Co
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C249/00—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton
    • C07C249/04—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of oximes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
    • C07C251/32—Oximes
    • C07C251/34—Oximes with oxygen atoms of oxyimino groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals
    • C07C251/44—Oximes with oxygen atoms of oxyimino groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals with the carbon atom of at least one of the oxyimino groups being part of a ring other than a six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/14—The ring being saturated

Definitions

  • the present invention relates to the production of oxirnes. More particularly, .the present invention relates to an economical process for obtaining cyclohexanone oxime.
  • Cyclohexanone oxime which 'finds its primary useas a precursor-for the polyamide intermediate, e-caprolac' cause' of increased use of the polymers .obtained from 5 caprolactam in. a variety of applications, improved, cheapermethods of obtaining the intermediate'cyclohexanone'oxime are needed.
  • Example I Seventeen parts of the potassium salt of nitrocyclohexane dissolved in parts of anhydrous methanol was chargedto a stainless steel bomb provided with a Pyrex (registered trademark of Coming Glass Works) glass liner.
  • the bomb was pressurized to 390 p.s.i.ga. with carbon monoxide and then to 600 p.s.i.ga. with hydrogen; "Agitation was started and the mixture heated to 180 C.
  • the mixture was maintained at 180-190 C. for 3 hours
  • the pressure was 440 p.s.i.ga., and the bomb wascooled and vented.
  • the bomb contents were re-' moved and thesolvent removedtherefrom by distillation under reduced pressure.
  • Example 2 The general procedure of Example 1 was used in the following runs:
  • an objectof the presentinvention is to Pressure (p.s.i.ga.) Yield of i i Reaccyclo- NCH parts .Aikanol parts Initial Final tion hexanone Salt Partial Diluent Initial Time oxime Pressure Gas Total (hrs;) (percent) of 00 Pressure Pressure Temp.
  • Another object of the present invention is to provide an improved process for the preparation of lactam intermediates wherein cheap, readily available reagents can be used.
  • nitrocyclohexane is caused to react with carbon monoxide and a lower alkanol, e.g., methanol or ethanol, in the presence of a base at temperatures between about 150 and about 200 C. and pressures between about 500 and about 900 p.s.i.ga.
  • a lower alkanol e.g., methanol or ethanol
  • An alkaline-salt of the nitrocyclohexane e.g., the sodium, potassium, or ammonium salt, preferably is used as the starting material in the present process.
  • the nitrocyclohexane preferably is used in the form of an alkaline salt.
  • alkaline salt in the present speci fication and claims is meant the alkali-metal salts, particularlythe potassium and sodium salts illustrated in the examples, and the ammonium salt. All of these salts are readily prepared by techniques well known in the art.
  • the nitrocyclohexane salt is caused to react with methanol or ethanol and carbon monoxide.
  • methanol or ethanol and carbon monoxide e.g., ethanol and carbon monoxide.
  • alkanols such as isopropanol, butanol, and the like.
  • Alkanols containing one to four carbon atoms are generally to'be preferred in the present process.
  • the pressure required for the process of the invention may be achieved with the carbon monoxide alone or with a mixture of carbon monoxide with an inert diluent gas such as hydrogen or nitrogen.
  • inert diluent gas is meant a gaseous sub stance which is inert to all the reaction components under the conditions of the reaction.
  • the total pressure used in the present process may vary between about 500 and about 900 p.s.i.ga. Pressures much below this range are operable but give very low yields of the oxime inreasonable periods of time. Y Higher pressures are unnecessary with respect to the yields obtained and require excessively expensive equipment.
  • the preferred initial-total pressure in the present; process is between about 600 and about800 p.s.i.ga.v p
  • My present process can be operated at temperatures between about 150 and about 200 C. Below about 150 C., the reaction is slow. Excessive decomposition occurs at temperatures much above 200?: C. ..Awnum-, ber of experiments on the present process, including those of the foregoing examples, have indicated that the best yields may he obtained when the temperature is maintained between about 180 and about 200 C. I have found that temperature control is simplified and, hence, that decomposition is minimized, by preheating to the reaction temperaturea mixture of the alkanol and carbon monoxide 'or carbon monoxide-diluent -gas introduced under. pressure and then adding to the hot mixture a solution of the nitrocyclohexane salt in the alkanol. v
  • reaction in the present process maybe complete within a period of between about two and about six hours .process to nitrocyclohexane.
  • nitro cycloalkanes such as nitrocyclopentane and secondary nitro alkanes such as Z-nitropropane also could be used.
  • the oxime obtained by the present process is readily converted to caprolactam .by the Beckmann rearrangement, for which many variations and techniques .are well known in the art.
  • the oxime also is useful as an insecticide, as a solvent, and asa chemical intermediate.
  • r v r 1 A process for the production of cyclohexanone oxime which comprises reacting an alkaline salt of nitrocylcohexane with at least equimolar amounts of carbon monoxide'and an alkanol containing one to four carbon atoms at temperatures between about and about 200 C. and pressures between about 500 and about 900 p.s.1.'ga.
  • a process for the production of cyclohexanone oxime which comprises reactingan alkaline salt of nitrocyclohexane with at least equimolar amounts of carbon monoxide and an alkanol containing one to four carbon atoms at temperatures between about 180 and about 200 C. and pressures between about 600 and about 800 p.s.1.ga.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Description

; 2,945,065 PROCESS ron THE REDUCTION F NITROCY- CLOHEXANE TO-CYCLOHEXANONE'OXIME Lorraine GuyDonaruma, Media, Pa., assignor to E. I. du Pont de Nemours and Company,-Wilmington, Del., a corporation of Delaware No Drawing. Filed July 30,1958,Ser.No.751,819
f 7 Claims. (Cl. 260-566) 1 The present invention relates to the production of oxirnes. More particularly, .the present invention relates to an economical process for obtaining cyclohexanone oxime.
Cyclohexanone oxime, which 'finds its primary useas a precursor-for the polyamide intermediate, e-caprolac' cause' of increased use of the polymers .obtained from 5 caprolactam in. a variety of applications, improved, cheapermethods of obtaining the intermediate'cyclohexanone'oxime are needed.
Patented July 12}, 19 69 nitrocyclohexane introduced less the moles of salt of nitrocyclohexane recovered.
Example I Seventeen parts of the potassium salt of nitrocyclohexane dissolved in parts of anhydrous methanol was chargedto a stainless steel bomb provided with a Pyrex (registered trademark of Coming Glass Works) glass liner. The bomb was pressurized to 390 p.s.i.ga. with carbon monoxide and then to 600 p.s.i.ga. with hydrogen; "Agitation was started and the mixture heated to 180 C. The mixture was maintained at 180-190 C. for 3 hours At the end of this period and at the reaction temperature, the pressure was 440 p.s.i.ga., and the bomb wascooled and vented. The bomb contents were re-' moved and thesolvent removedtherefrom by distillation under reduced pressure. 'Water was added to the distillation residue and the pH adjusted to 5. The mixture was extracted with ether, the ether extract dried, and the solvent partially removed from the dried extract by' distillation. The residue was extracted With 20% sulfuric acid, and the pH of the acid extract was adjusted to 5. The ether extraction and solvent removal procedures were repeated. The distillation residue was crystalline cyclohexanone oxime which was obtained in a yield Example 2 The general procedure of Example 1 was used in the following runs:
, Accordingly, an objectof the presentinvention is to Pressure (p.s.i.ga.) Yield of i i Reaccyclo- NCH parts .Aikanol parts Initial Final tion hexanone Salt Partial Diluent Initial Time oxime Pressure Gas Total (hrs;) (percent) of 00 Pressure Pressure Temp.
15. 1 OH OH..- 50 380 H:-- 700 b 718 180-190 2. 5 43 17 CzH5QH.- 20 600 600 620 180-200 2.5 65 OH O 1600' 250 N, 600 180-490 2 46 1 N (DH-nitrocyclohexane.
hMax. pressure attained during run was 760 p.s.i.ga.
Max. pressure attained-d d Not recorded.
provide an economical process for obtaining cyclohexanone oxime.
"Another object of the present invention is to provide an improved process for the preparation of lactam intermediates wherein cheap, readily available reagents can be used.
Other objects will become apparent from the following detailed description of the invention.
I have found that the foregoing objects may be achieved when nitrocyclohexane is caused to react with carbon monoxide and a lower alkanol in the presence of a base under conditions of elevated temperature and pressure.
In accordance with the process of the present invention, nitrocyclohexane is caused to react with carbon monoxide and a lower alkanol, e.g., methanol or ethanol, in the presence of a base at temperatures between about 150 and about 200 C. and pressures between about 500 and about 900 p.s.i.ga. An alkaline-salt of the nitrocyclohexane, e.g., the sodium, potassium, or ammonium salt, preferably is used as the starting material in the present process.
The present process is illustrated by the following examples, but the invention is not to be construed as limited to the specific techniques shown therein. The parts in the examples are parts by weight, and the yields reported express the relationship between the moles of product cyclohexanone oxime obtained and the moles of salt of uring run was 800 p.s.i.ga.
valuable polymer precursor. As was stated in the fore-.
going, the nitrocyclohexane preferably is used in the form of an alkaline salt. By alkaline salt in the present speci fication and claims is meant the alkali-metal salts, particularlythe potassium and sodium salts illustrated in the examples, and the ammonium salt. All of these salts are readily prepared by techniques well known in the art.
In the embodiments shown in the examples, the nitrocyclohexane salt is caused to react with methanol or ethanol and carbon monoxide. However, depending on economic considerations, I can use other alkanols such as isopropanol, butanol, and the like. Alkanols containing one to four carbon atoms are generally to'be preferred in the present process.
As is illustrated in the examples, the pressure required for the process of the invention may be achieved with the carbon monoxide alone or with a mixture of carbon monoxide with an inert diluent gas such as hydrogen or nitrogen. By inert diluent gas is meant a gaseous sub stance which is inert to all the reaction components under the conditions of the reaction.
The total pressure used in the present process may vary between about 500 and about 900 p.s.i.ga. Pressures much below this range are operable but give very low yields of the oxime inreasonable periods of time. Y Higher pressures are unnecessary with respect to the yields obtained and require excessively expensive equipment. The preferred initial-total pressure in the present; process is between about 600 and about800 p.s.i.ga.v p
My present process can be operated at temperatures between about 150 and about 200 C. Below about 150 C., the reaction is slow. Excessive decomposition occurs at temperatures much above 200?: C. ..Awnum-, ber of experiments on the present process, including those of the foregoing examples, have indicated that the best yields may he obtained when the temperature is maintained between about 180 and about 200 C. I have found that temperature control is simplified and, hence, that decomposition is minimized, by preheating to the reaction temperaturea mixture of the alkanol and carbon monoxide 'or carbon monoxide-diluent -gas introduced under. pressure and then adding to the hot mixture a solution of the nitrocyclohexane salt in the alkanol. v
While I- do not wish to be limited-by any theoretical discussions, I believe that the alkyl cyclohexanenitronate corresponding to the alkanol used may be an intermediate to the cyclohexanone oxime obtained by the process of the present invention. Thus, the present process may be illustrated by the equation:
+ o-i-omon Pressure OK Although, as the foregoing equation indicates, only equimolar amounts of the nitrocyclohexane salt, the carbon monoxide, and the alkanol are theoretically required Y excess of the gaseous carbon monoxide or carbon monoxide-diluent mixture facilitates agitation and intimate mixing of the reactants.
Depending generally on'the reaction conditions chosen,
the reaction in the present process maybe complete within a period of between about two and about six hours .process to nitrocyclohexane.
applicability of the present However, other nitro cycloalkanes such as nitrocyclopentane and secondary nitro alkanes such as Z-nitropropane also could be used.
The oxime obtained by the present process is readily converted to caprolactam .by the Beckmann rearrangement, for which many variations and techniques .are well known in the art. The oxime also is useful as an insecticide, as a solvent, and asa chemical intermediate.
' The present process has been described in detail in the foregoing, but many variations will be apparent to those skilled in the art. Hence, I intend to be limited only by the following claims. r v r 1. A process for the production of cyclohexanone oxime which comprises reacting an alkaline salt of nitrocylcohexane with at least equimolar amounts of carbon monoxide'and an alkanol containing one to four carbon atoms at temperatures between about and about 200 C. and pressures between about 500 and about 900 p.s.1.'ga.
2. The process asclaimed in claim 1, wherein the alkaline salt, ofnitrocyclohexane is the sodium salt.
3. The process as claimed in claim 1, wherein the alkaline salt of nitrocyclohexane is the potassium salt.
4. The process as claimed in claim 1, wherein the alkanol is methanol.
' 5. The process as claimed in claim 1, wherein the alkanol is ethanol.
6. A process for the production of cyclohexanone oxime which comprises reactingan alkaline salt of nitrocyclohexane with at least equimolar amounts of carbon monoxide and an alkanol containing one to four carbon atoms at temperatures between about 180 and about 200 C. and pressures between about 600 and about 800 p.s.1.ga.
7. The process as claimed in claim 6, wherein the carbon monoxide is mixed with an inert diluent gas selected from the group consisting of hydrogen and nitrogen.
,1 have illustrated the References Cited in the file of this patent UNITED STATES PATENTS Germany May 21, 1953

Claims (1)

1. A PROCESS FOR THE PRODUCTION OF CYCLOHEXANONE OXIME WHICH COMPRISES REACTING AN ALKALINE SALT OF NITROCYLCOHEXANE WITH AT LEAST EQUIMOLAR AMOUNTS OF CARBON MONOXIDE AND AN ALKANOL CONTAINING ONE TO FOUR CARBON ATOMS AT TEMPERATURES BETWEEN ABOUT 150 AND ABOUT 200* C. AND PRESSURES BETWEEN ABOUT 500 AND ABOUT 900 P.S.I.GA.
US751819A 1958-07-30 1958-07-30 Process for the reduction of nitrocy-clohexane to cyclohexanone oxime Expired - Lifetime US2945065A (en)

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3129155A (en) * 1960-09-26 1964-04-14 Toyo Rayon Co Ltd Method of producing cycloalkanoneoxime hydrochlorides
US3218247A (en) * 1961-05-02 1965-11-16 Toyo Rayon Co Ltd Photochemical method of producing cycloalkanoneoxime hydrochlorides
US3341589A (en) * 1965-07-06 1967-09-12 Commercial Solvents Corp Process for preparing oximes
US3341590A (en) * 1965-07-06 1967-09-12 Commercial Solvents Corp Process for preparing oximes
US3341588A (en) * 1965-07-06 1967-09-12 Commercial Solvents Corp Process for preparing oximes
US3480672A (en) * 1967-03-28 1969-11-25 Olin Mathieson Process for reduction of nitro compounds to corresponding oximes and ketones
US3981916A (en) * 1970-07-09 1976-09-21 Texaco Inc. Reduction of nitroparaffin substrates to their corresponding oximes using a silver salt catalyst
US3989755A (en) * 1973-06-21 1976-11-02 Atlantic Richfield Company Production of oximes by the reaction of carbon monoxide with nitrocompounds

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2638482A (en) * 1951-01-25 1953-05-12 Olin Mathieson Production of cyclohexanone oxime
DE877303C (en) * 1951-11-04 1953-05-21 Basf Ag Process for the preparation of oximes
US2702301A (en) * 1953-03-06 1955-02-15 Basf Ag Production of colorless salts of aci-nitro compounds
US2711427A (en) * 1953-09-21 1955-06-21 Monsanto Chemicals Production of cyclohexanone oxime
US2763686A (en) * 1955-06-30 1956-09-18 Du Pont Production of oximes

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2638482A (en) * 1951-01-25 1953-05-12 Olin Mathieson Production of cyclohexanone oxime
DE877303C (en) * 1951-11-04 1953-05-21 Basf Ag Process for the preparation of oximes
US2702301A (en) * 1953-03-06 1955-02-15 Basf Ag Production of colorless salts of aci-nitro compounds
US2711427A (en) * 1953-09-21 1955-06-21 Monsanto Chemicals Production of cyclohexanone oxime
US2763686A (en) * 1955-06-30 1956-09-18 Du Pont Production of oximes

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3129155A (en) * 1960-09-26 1964-04-14 Toyo Rayon Co Ltd Method of producing cycloalkanoneoxime hydrochlorides
US3218247A (en) * 1961-05-02 1965-11-16 Toyo Rayon Co Ltd Photochemical method of producing cycloalkanoneoxime hydrochlorides
US3341589A (en) * 1965-07-06 1967-09-12 Commercial Solvents Corp Process for preparing oximes
US3341590A (en) * 1965-07-06 1967-09-12 Commercial Solvents Corp Process for preparing oximes
US3341588A (en) * 1965-07-06 1967-09-12 Commercial Solvents Corp Process for preparing oximes
US3480672A (en) * 1967-03-28 1969-11-25 Olin Mathieson Process for reduction of nitro compounds to corresponding oximes and ketones
US3981916A (en) * 1970-07-09 1976-09-21 Texaco Inc. Reduction of nitroparaffin substrates to their corresponding oximes using a silver salt catalyst
US3989755A (en) * 1973-06-21 1976-11-02 Atlantic Richfield Company Production of oximes by the reaction of carbon monoxide with nitrocompounds

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